KR101660520B1 - Method of performing continuous electroless plating of copper and nickel and plating layer using the same - Google Patents
Method of performing continuous electroless plating of copper and nickel and plating layer using the same Download PDFInfo
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- KR101660520B1 KR101660520B1 KR1020150049777A KR20150049777A KR101660520B1 KR 101660520 B1 KR101660520 B1 KR 101660520B1 KR 1020150049777 A KR1020150049777 A KR 1020150049777A KR 20150049777 A KR20150049777 A KR 20150049777A KR 101660520 B1 KR101660520 B1 KR 101660520B1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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Abstract
Description
Technical aspects of the present invention relate to electroless plating, and more particularly, to a continuous electroless plating method of copper and nickel.
As the use of electronic devices increases, radio waves generated from such electronic devices interfere with each other, resulting in errors in detection or analysis of desired signals, thereby degrading malfunction and performance of electronic devices. This phenomenon is referred to as EMI (Electromagnetic Interference). Such electromagnetic interference can cause diseases due to unbalance of the body temperature and biorhythm of the human body at the time of prolonged exposure. In case of severe brain cancer, cancer, leukemia And the like. For this reason, in developed countries, regulations on electromagnetic interference are being strengthened, and there is growing interest in techniques for shielding electromagnetic interference.
BACKGROUND ART [0002] As a method of shielding electromagnetic interference, researches on materials capable of protecting electronic parts and human bodies from electromagnetic waves have been actively conducted. For example, non-conductive materials such as plastic, paper, and fibers can transmit electromagnetic waves without blocking them, so that the materials can be metallized to impart an electromagnetic wave shielding function. There are various methods for shielding electromagnetic waves from nonconductive materials. For example, methods such as coating a conductive paint on a surface, plating a metal, or forming an electrolytic conductive plastic composite molding compound are used.
As the metal plating method of the nonconductive material, an electroless plating method is generally used, and nickel or copper is mainly used as the metal. However, since the plating solution used in the electroless plating method uses toxic harmful substances to the human body such as ammonia or formalin, there is an increasing demand for a plating solution which does not use such harmful substances.
The technical problem to be solved by the technical idea of the present invention is to provide a continuous electroless plating method of copper and nickel without using formalin and ammonia.
Another object of the present invention is to provide a plating layer formed by the continuous electroless plating method of copper and nickel.
However, these problems are illustrative, and the technical idea of the present invention is not limited thereto.
According to an aspect of the present invention, there is provided a continuous electroless plating method for copper and nickel, comprising: providing a plating object; Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer; And immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer.
In some embodiments of the present invention, the electroless copper plating solution and the electroless nickel plating solution may have basicity.
In some embodiments of the present invention, the first reducing agent may be a mixture of two or more and five or less species.
In some embodiments of the present invention, the first complexing agent may be a mixture of two or more and five or less kinds of substances.
In some embodiments of the present invention, the electroless copper plating solution may be maintained at a temperature ranging from 10 캜 to 70 캜.
In some embodiments of the present invention, the electroless nickel plating solution may be maintained at a temperature ranging from 20 캜 to 90 캜.
In some embodiments of the present invention, the nickel metal salt may be included in the range of 1 g to 10 g per 1 liter of the electroless nickel plating solution.
In some embodiments of the present invention, the second reducing agent comprises at least any one of sodium hypophosphite, potassium hypophosphite, and ammonium hypophosphite, and is used in an amount of 1 g to 100 g . ≪ / RTI >
In some embodiments of the present invention, the second complexing agent comprises a carboxylic acid and a derivative thereof, and may be included in the range of 1 g to 100 g per 1 liter of the electroless nickel plating solution.
In some embodiments of the present invention, the second complexing agent may be a mixture of two or more and five or less kinds of substances.
In some embodiments of the present invention, the second complexing agent comprises glycine in the range of 2 g to 30 g, and may include any of citric acid, tartaric acid, and succinic acid in the range of 2 g to 30 g .
In some embodiments of the present invention, the second pH adjusting agent comprises at least one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, and diethylenetriamine can do.
In some embodiments of the present invention, the electroless nickel plating solution may have a pH in the range of 7.5 to 12.
In some embodiments of the present invention, the electroless copper plating solution contains copper sulfate as the copper metal salt, and copper ions in the electroless copper plating solution are adjusted to a concentration of 3 g per liter of the electroless copper plating solution Wherein the first reducing agent comprises 20 g of sodium hypophosphite per liter of the electroless copper plating solution and 5 g of glyoxylic acid per liter of the electroless copper plating solution, Ten grams of N, N, N, N'-tetrakis (2-hydroxypropyl) ethylenediamine (THPED) and 1 liter of the electroless copper plating solution were added to 1 liter of the electroless copper plating solution, Wherein the stabilizer comprises 2 mg of sodium cyanide per liter of the electroless copper plating solution, the temperature of the electroless copper plating solution is 50 캜, and the pH is 12.5.
In some embodiments of the present invention, the electroless nickel plating solution contains nickel sulfate as the nickel metal salt, and the nickel ion in the electroless nickel plating solution has a concentration of 4 g per 1 liter of the electroless nickel plating solution And the second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution and the second complexing agent comprises 5 g of citric acid and 1 g of potassium carbonate per liter of the electroless nickel plating solution, 5 g of glycine was contained per 1 liter of the electroless nickel plating solution, the temperature of the electroless nickel plating solution was 50 캜, and the pH was 9.
In some embodiments of the present invention, the electroless nickel plating solution contains nickel sulfate as the nickel metal salt, and the nickel ion in the electroless nickel plating solution has a concentration of 4 g per 1 liter of the electroless nickel plating solution And the second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution and the second complexing agent comprises 5 g of tartaric acid per 1 liter of the electroless nickel plating solution, 5 g of glycine was contained per 1 liter of the electroless nickel plating solution, the temperature of the electroless nickel plating solution was 50 캜, and the pH was 9.
In some embodiments of the present invention, the electroless nickel plating solution contains nickel sulfate as the nickel metal salt, and the nickel ion in the electroless nickel plating solution has a concentration of 4 g per 1 liter of the electroless nickel plating solution And the second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution and the second complexing agent comprises 5 g of citric acid and 1 g of potassium carbonate per liter of the electroless nickel plating solution, The electroless nickel plating solution contains 15 g of glycine per 1 liter of the electroless nickel plating solution. The temperature of the electroless nickel plating solution may be 50 캜 and the pH may be 9.
In some embodiments of the present invention, the electroless nickel plating solution contains nickel sulfate as the nickel metal salt, and the nickel ion in the electroless nickel plating solution has a concentration of 4 g per 1 liter of the electroless nickel plating solution And the second reducing agent comprises 16 g of sodium hypophosphite per liter of the electroless nickel plating solution and the second complexing agent contains 10 g of succinic acid per liter of the electroless nickel plating solution , The temperature of the electroless nickel plating solution is 50 캜, and the pH is 9.
In some embodiments of the present invention, the electroless copper plating solution may exclude formalin, and the electroless nickel plating solution may exclude ammonia.
In some embodiments of the present invention, in order to improve the lifetime of the electroless nickel plating solution and the luster of the nickel plating layer, at a time when nickel ions in the electroless nickel plating solution are consumed 1/10 to 1/2 times, (Tl) may be added in an amount of 0.1 to 2.0 ppm.
In order to accomplish the above object, the plating layer according to the technical idea of the present invention is formed by the above-described continuous electroless plating method of copper and nickel.
The continuous electroless plating method of copper and nickel according to the technical idea of the present invention is a method of continuously forming a copper plating layer and a nickel plating layer on a nonconductive plating object by using an electroless copper plating liquid excluding formalin and an electroless nickel plating liquid excluding ammonia can do.
In performing electroless copper plating, by using sodium hypophosphite, glyoxylic acid, or the like instead of formalin which is conventionally used as a reducing agent, it is possible to form a copper plating layer having excellent properties while ensuring stability of the plating liquid, And the use of formaldehyde, which is harmful to the environment, can be essentially eliminated.
In addition, during the electroless nickel plating, by using citric acid, glycine, tartaric acid, succinic acid, or the like instead of ammonia, which is commonly used as a pH adjuster, a nickel plating layer having excellent properties is formed while securing stability of the plating solution, It is possible to fundamentally eliminate the use of ammonia which increases the lifetime and harms the operator and the environment.
The continuous electroless plating method of copper and nickel according to the technical idea of the present invention can effectively form a plating layer on a nonconductive plating object and thus can produce an electromagnetic wave shielding fiber product and the like, It can be used in various industrial fields such as electromagnetic shielding agents for electromagnetic wave shielding of industrial and electronic parts, static eliminators, surface heating elements, and functional clothes.
The effects of the present invention described above are exemplarily described, and the scope of the present invention is not limited by these effects.
1 is a flow chart showing a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
2 is a photomicrograph showing a copper plating layer formed using a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
3 is a photomicrograph showing a nickel plating layer formed using a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
FIG. 4 is a photograph showing color change of an electroless nickel plating solution used in a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
FIG. 5 is a graph showing the weight of the plating layer formed on the electroless nickel plating solution used in the continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. The scope of technical thought is not limited to the following examples. Rather, these embodiments are provided so that this disclosure will be more thorough and complete, and will fully convey the scope of the invention to those skilled in the art. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The same reference numerals denote the same elements at all times. Further, various elements and regions in the drawings are schematically drawn. Accordingly, the technical spirit of the present invention is not limited by the relative size or spacing depicted in the accompanying drawings. In addition, the following terms "first" and "second" are used for simply distinguishing constituents and do not mean order, priority, importance or the like. In the present invention, the component corresponding to the electroless copper plating solution is referred to as "first" and the electroless nickel plating solution (hereinafter referred to as " first component ") is used for distinguishing constituent elements having the same name, Quot; second ".< / RTI >
The technical idea of the present invention is to provide a nickel electroless plating method and a copper electroless plating method which do not use substances harmful to human bodies such as ammonia and formalin.
Among the methods for shielding electromagnetic waves, the metal plating method is a method of shielding electromagnetic waves by forming a metal plating layer of aluminum, iron, tin, zinc, copper, nickel, silver or the like on the surface of fiber or plastic. Such a metal plating layer is excellent in electromagnetic wave shielding effect and is also excellent in productivity.
The method of forming the metal plating layer can be classified into a dry method and a wet method. In the wet method, a noble metal catalyst such as palladium or silver is deposited on the surface of a non-conductive material such as plastic or fiber, and then a metal surface is formed by electroless plating. Such a wet process can provide an excellent electromagnetic wave shielding effect because the metal plating layer can be uniformly formed on the surface of the nonconductive material.
Electroless plating is a method of spontaneous oxidation of materials in a plating solution without the need for external power. And precipitation of the material occurs by the reduction reaction to form a plating layer. The electroless copper plating solution may further contain a metal salt, a complexing agent, a reducing agent and the like for providing copper ions, and may further comprise a pH adjuster, a solution stabilizer, a surfactant, and the like. Since the electroless plating is performed in the plating liquid as in the case of electroplating, it is excellent in the process continuity with the subsequent electrolytic plating, and the liquid plating solution can easily penetrate into the pattern, thereby providing a uniform step coverage , A copper plating layer having excellent characteristics can be formed. Further, the electroless plating can be directly applied to the element layer by electrodeposition of a conductor layer by applying organic additives such as an accelerator, an inhibitor, and a leveler used in a seed layer formation and electroplating.
Since the electroless plating uses the chemical driving force of the chemical substances in the plating liquid, unlike the electrolytic plating which is provided with the electric driving force from the outside, the nonconductive plating object is subjected to pretreatment such as etching, surface activation, It is necessary to make it possible to perform plating. The pretreatment solution for pretreatment can be an acidic solution or a basic solution. For the stability and life of the plating solution and the stability of the plating layer, it is preferable to use an acidic solution for the plating solution when an acidic solution is used as the pretreatment solution. In the case of using a basic solution as the pretreatment solution, Is preferably used. In general, the acidic solution is mainly used at a high temperature, and there is a limit to the consumption of the plating solution due to the elevated temperature. Thus, a basic solution is used as the pretreatment solution and a basic solution is used as the plating solution. Particularly, in order to prevent deformation of the plating target and to stabilize the plating solution, it is common to use a low-temperature alkaline plating solution in the case of a plating target of fiber, plastic or semiconductor material.
1 is a flowchart showing a continuous electroless plating method (S100) of copper and nickel according to an embodiment of the present invention.
Referring to FIG. 1, a continuous electroless plating method (S100) of copper and nickel includes the steps of: providing a nonconductive plating object (S110); Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer (S120); And a step (S130) of immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer .
The step of forming the copper plating layer (S120) and the step of forming the nickel plating layer (S130) may be continuously performed. This is because the electroless copper plating solution and the electroless nickel plating solution according to the technical idea of the present invention all have a basicity so that it is possible to prevent an unnecessary acid base reaction and thus an intermediate treatment step such as washing can be omitted, Thereby enabling a continuous process.
The plating object may be a metal or a non-metal, and may be a conductive material or a non-conductive material. The plating object may include, for example, a silicon wafer, a polymer film, plastic, fiber, paper and the like. The plating target may be a structure having an insulating layer formed thereon, for example, a silicon wafer having a diffusion barrier layer such as tantalum or ruthenium formed thereon, and may be a printed circuit board (PCB), for example.
Hereinafter, the electroless copper plating solution according to the technical idea of the present invention will be described in detail.
Generally, an electroless copper plating solution is used in a basic region. In addition, although a plating solution using formaldehyde or formalin as a reducing agent is generally widely used, such formaldehyde or formalin is a toxic substance which causes environmental pollution, and the odor and working environment caused by the temperature rise of the electroless copper plating solution are lowered And the stability of the plating solution is decreased in the continuous production process for a long time, so that spontaneous decomposition easily occurs.
According to the technical idea of the present invention, the electroless copper plating solution may include a solvent, and a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer dissolved in the solvent.
The electroless copper plating solution may be basic.
The electroless copper plating solution may be maintained at a temperature ranging, for example, from about 10 캜 to about 70 캜, for example, at a temperature ranging from about 20 캜 to about 70 캜, , ≪ / RTI > at a temperature in the range of from about 20 DEG C to about 60 DEG C. When the temperature of the electroless copper plating solution is low, a plating rate is low but a dense plating layer can be obtained. When the temperature of the electroless copper plating solution is high, the plating rate is high. Therefore, It can be adjusted by using the temperature of the electroless copper plating solution. If the temperature of the electroless copper plating solution is higher than 70 ° C, the stability of the plating solution may decrease and the lifetime thereof may be reduced.
The electroless copper plating solution may contain water as the solvent. However, it is to be understood that the technical idea of the present invention is not limited thereto, and the use of other materials as a solvent is included in the technical idea of the present invention.
According to the technical idea of the present invention, the electroless copper plating solution may exclude formalin conventionally used as the first reducing agent.
The electroless copper plating solution may include a copper metal salt that provides copper ions. The copper metal salt may include, for example, copper sulfate, copper chloride, copper nitrate, copper acetate, copper pyrophosphate, and copper sulfamate, and mixtures thereof.
The copper metal salt may be contained in the range of, for example, about 0.5 g to about 50 g, and for example, in the range of about 1 g to about 20 g per liter of the electroless copper plating solution, For example, in the range of about 1 g to about 5 g.
The electroless copper plating solution may include the first reducing agent for reducing copper ions provided from the copper metal salt. The first reducing agent may include, for example, an aldehyde derivative, a reducing sugar having an aldehyde group, a reducing sugar having a ketone group, or a phosphate derivative. The first reducing agent may be selected from the group consisting of glyoxal, methylglyoxal, ethylglyoxal, benzaldehyde, glucose, fructose, galactose, maltose, lactose, phosphinic acid (HPH 2 O 2 ) , Hypophosphorous acid (H 4 P 2 O 6 ), sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, sodium borohydride, and the like, and mixtures thereof. Particularly, the first reducing agent may exclude formaldehyde aqueous solution and formalin.
The first reducing agent may be contained in the range of, for example, about 1 g to about 100 g, and for example, about 2 g to about 50 g, per 1 liter of the electroless copper plating solution. When such a first reducing agent is contained in an amount of less than 2 g or 50 g or more per 1 liter of the electroless copper plating solution, the stability of the electroless copper plating solution and the plating rate can be lowered.
When the first reducing agent does not include an aqueous solution of formaldehyde, if the first reducing agent includes one kind of the first reducing agent, the plating reaction may stop for a certain period of time after the start of plating. However, the first reducing agent can be a mixture of two or more materials among the above-mentioned materials, and in this case, the plating reaction can be prevented from being stopped. For example, the reducing agent may be a mixture of two or more and five or less species.
The electroless copper plating solution may include the first complexing agent which facilitates the reduction reaction of copper by forming a complex with the copper ion provided from the copper metal salt. The first complexing agent may include, for example, a polycarboxylic acid including a hydroxyl group, an amino acid including a carboxyl group, a diamine including a hydroxyl group, or a monoamine including a hydroxyl group. The first complexing agent may be selected from the group consisting of, for example, tatrate, rochelle salt, citrate, ethylenediaminetetraacetic acid (EDTA), pentetinic acid (DTPA, N, N, N'-tetrakis (2-hydroxypropyl) ethylenediamine (THPED), N, N'-tetramethylethylenediaminetetraacetic acid (NTA),
The first complexing agent may be included in the range of, for example, about 1 g to about 150 g, and for example, in the range of about 10 g to about 100 g, per liter of the electroless copper plating solution . If the first complexing agent is less than or more than the above-mentioned range, the stability of the electroless copper plating solution may be lowered, and the electroless copper plating solution may spontaneously decompose or adversely affect the formation of the copper plating layer and the plating speed. The first complexing agent may be formed by mixing two or more materials among the above-mentioned materials, for example, two or more materials to four or less materials or two or more materials to five or less materials or more Further, five or more kinds of materials may be mixed and formed.
The electroless copper plating solution may include a first pH adjusting agent for adjusting the pH of the electroless copper plating solution. Since the plating layer formed on the plating object is affected by the plating speed and the thickness of the plating layer due to the pH of the electroless copper plating solution, it is preferable that the electroless copper plating solution is added with a substance capable of maintaining and controlling pH of the electroless copper plating solution Do. Accordingly, the first pH adjusting agent may be added to the electroless copper plating solution as a substance that performs such a function. The first pH adjusting agent may include an inorganic acid or a salt thereof such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, diethylenetriamine, and the like.
The first pH adjusting agent can maintain the pH of the electroless copper plating solution at a basic level, for example, the pH range can be maintained at 7.5 to 12, for example, the pH range can be maintained at 8 to 11, For example, the pH range can be maintained between 8.5 and 10.5. If the pH value of the electroless copper plating solution is less than 8.0 or more than 11, the plating rate may decrease and the properties of the plating layer may be deteriorated or the stability of the plating solution may be decreased.
The stabilizer may be added for preventing stabilization oxidation of the electroless copper plating solution, providing uniform plating precipitation, controlling the plating rate, and improving physical properties of the plating layer. The stabilizer may include various stabilizers.
The stabilizer may be at least one selected from the group consisting of polyoxyethylene cetyl ether, glycerol ester, sorbitan ester, nonylphenol ether, polyethylene oxide (PEO), polyethylene oxide (PEO) PPO), polyoxyethylene thioether, and the like, and mixtures thereof.
In order to prevent the spontaneous decomposition of the electroless copper plating solution, the stabilizer may include sodium cyanide, cyanamide, and propionitrile as cyanide, sodium chloride, ammonium chloride, and potassium chloride as chlorine compounds, potassium sulfide as inorganic sulfur compounds, Sodium thiosulfate, sodium sulfide, thiocyanate, thiol as an organic sulfide, mercaptan compound as a mercaptan compound, mercaptobenzothiazole, mercaptothiazole, mercaptobenzimidazole, mercaptobenzoxazole, trithiocyanuric acid, Ethyl thiourea, ethyl thiocarbamate, thiourea, arithio urea, phenylthiourea, tetramethylthiourea, arylthiourea, and aminothiourea, indole derivatives such as pyridine derivatives as nitrogen compounds, 2,2-bipyridine, , Aminopyridine, phenanthroline, picolinic acid, and isonicotinic acid, and the like, and mixtures thereof. All.
The stabilizers may also include compounds of group 16 (Group 6A), sulfur, selenium, and tellurium, and the like, to reduce copper nucleation energy, and mixtures thereof . ≪ / RTI >
The stabilizer may include bromine, iodine, antimony, lead, mercury, tin, cerium, europium, thorium and the like as the surfactant element and may include a compound thereof and a mixture thereof can do.
The stabilizer may include a hydrogen embrittlement inhibitor of a copper plating layer and may include a cyanide salt such as sodium cyanide, potassium cyanide, ammonium cyanide, acetonitrile, potassium hexacyanoferrate, potassium isocyanate, And mixtures thereof.
In addition, the stabilizer may include adenine, cytosine, guanine, guanidine, benzotriazole, mercaptobenzothiazole, mercaptopyridine, diethyldithiocarbamic acid, and mercaptotripyrimidine as the sensitizer And mixtures thereof.
The stabilizer may be included in the range of about 0.0001 g to about 10 g, for example, in the range of about 0.0002 g to about 1 g, for 1 liter of the electroless copper plating solution. If the amount of the stabilizer is less than or more than the above-mentioned range, the gloss of the electroless copper plating solution may decrease or a plating stop phenomenon may occur.
Hereinafter, the electroless nickel plating solution according to the technical idea of the present invention will be described in detail.
Generally, the electroless nickel plating solution can be classified into an acid plating solution, an ammonia basic plating solution, and a sodium hydroxide basic plating solution. The ammonia basic plating solution has a bad odor and bad working environment, and the sodium hydroxide basic plating solution causes a white precipitate in a basic region, requiring a large amount of a complexing agent. At this time, citrate is most commonly used as a complexing agent in consideration of complex formation characteristics and plating rate in the plating liquid. Further, the characteristics of the plating layer may be changed depending on the complexing agent, the adjusting agent and the pH buffer added in the electroless nickel plating solution.
According to the technical idea of the present invention, the electroless nickel plating solution may include a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent.
The electroless nickel plating solution may be basic.
The electroless nickel plating solution may be maintained at a temperature ranging, for example, from about 20 캜 to about 90 캜, for example, at a temperature ranging from about 40 캜 to about 70 캜. When the temperature of the electroless nickel plating solution is low, the plating rate is low. When the temperature of the electroless nickel plating solution is high, the plating rate is high. Therefore, the temperature of the electroless nickel plating solution .
The electroless nickel plating solution may contain water as the solvent. However, it is to be understood that the technical idea of the present invention is not limited thereto, and the use of other materials as a solvent is included in the technical idea of the present invention.
According to the technical idea of the present invention, the electroless nickel plating solution may exclude ammonia which is conventionally used as the pH adjusting agent.
The electroless nickel plating solution may include a nickel metal salt that provides nickel ions. The nickel metal salt may include, for example, nickel sulfate, nickel chloride, nickel sulfide, nickel nitrate, nickel oxide, nickel carbonate, and the like, and may include a mixture thereof. For example, the nickel sulfate can be obtained by dissolving nickel, nickel oxide, or nickel carbonate in sulfuric acid and evaporating it at room temperature, thereby precipitating in a green needle crystal (orthorhombic) of the rhizome.
The nickel metal salt may be included, for example, in the range of about 1 g to about 10 g, and for example, in the range of about 1 g to about 5 g per liter of the electroless nickel plating solution. When the concentration of the nickel metal salt is less than 1 g / liter, a dense plated layer can be formed, but the plating rate may be significantly lowered. When the concentration of the nickel metal salt exceeds 5 g / liter, the plating rate is slightly increased, but a coarse plating layer may be formed and the stability of the nickel plating solution may be lowered, resulting in spontaneous decomposition of the electroless nickel plating solution.
The electroless nickel plating solution may include a second reducing agent for reducing the nickel ion provided from the nickel metal salt. The second reducing agent may be selected from the group consisting of phosphinic acid (HPH 2 O 2 ), hypophosphorous acid (H 4 P 2 O 6 ), hypophosphite, boron hydride, dimethylamine borane, hydrazine, and the like, and mixtures thereof. The second reducing agent may include at least one of sodium hypophosphite, potassium hypophosphite, and ammonium hypophosphite as the hypophosphite.
The second reducing agent may be included in the range of, for example, about 1 g to about 100 g, and for example about 2 g to about 50 g, per 1 liter of the electroless nickel plating solution. When such a second reducing agent is contained in an amount of less than 2 g or 50 g or more per liter of the electroless nickel plating solution, the stability of the electroless nickel plating solution and the plating rate can be lowered.
The electroless nickel plating solution may include the second complexing agent which forms a complex with the nickel ion provided from the nickel metal salt to facilitate the reduction reaction of nickel. For example, the second complexing agent may be chemically bonded to the nickel ion to form a nickel complex. The stability characteristics of the electroless nickel plating solution and the characteristics of the plating layer vary greatly depending on the kind and amount of the second complexing agent. Therefore, it is very important to select the type and amount of the second complexing agent depending on the purpose and use of the second complexing agent. The second complexing agent controls the plating rate, prevents spontaneous decomposition of the electroless nickel plating solution, and controls the plating reaction so that the reduction reaction of nickel occurs smoothly on the surface of the plating target. The second complexing agent can control the total amount of nickel ions participating in the reduction reaction with organic acids or their salts and prevent the nickel ions from being precipitated as nickel phosphate by binding with phosphorus, So that it is possible to perform the function of maintaining the stability during the operation. In addition, the second complexing agent can reduce the rapid generation of hydrogen ions by the reduction reaction, so that the pH of the electroless nickel plating solution can be prevented from changing abruptly.
The second complexing agent may include, for example, carboxylic acid and derivatives thereof, and may be, for example, a carboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a hydrocarboxylic acid, a thiocarboxylic acid, Or an aminocarboxylic acid. The second complexing agent may be, for example, acetic acid, formic acid, oxalic acid, chromoacetic acid, lactic acid, propionic acid, adipic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, glutaconic acid, itaconic acid, , Malonic acid, oxalacetic acid, phthalic acid, citric acid, azocitric acid, aconitic acid, tricarvalic acid, trimesic acid, melissic acid, malic acid, glycolic acid, glycine, mandelic acid, thioglycolic acid, Pio ninsan, thio Malak acid, Merck kepto propionitrile ninsan, alanine, arginine, aspartic acid, glutamic acid, cysteine acid, methionine, thio oxalic acid, glyoxylic acid, maleic acid, tartrate (tatrate), Lot selyeom (rochelle salt, Potassium tartarate, sodium potassium tartrate, and triethanolamine, and the like, and mixtures thereof.
The second complexing agent may be included in the range of, for example, about 1 g to about 100 g, and for example about 5 g to about 30 g, per 1 liter of the electroless nickel plating solution . If the second complexing agent is less than or more than the above-mentioned range, the stability of the electroless nickel plating solution is lowered, and the electroless nickel plating solution may be spontaneously decomposed, or the formation of the nickel plating layer and the plating rate may be adversely affected. The second complexing agent may be formed by mixing two or more kinds of materials among the above-mentioned materials, and may include, for example, two or more kinds of materials to four or less types of materials or two or more kinds of materials to five or less types of materials or more Further, five or more kinds of materials may be mixed and formed.
For example, the second complexing agent may include glycine in the range of about 2 g to about 30 g, and may be in the range of about 2 g to about 30 g, based on 1 liter of the electroless nickel plating solution, of citric acid, Or the like.
The electroless nickel plating solution may include a second pH adjusting agent for adjusting the pH of the electroless nickel plating solution. Since the plating layer formed on the plating object is affected by the plating speed and the thickness of the plating layer depending on the pH of the electroless nickel plating solution, it is preferable that the electroless nickel plating solution is added with a substance capable of maintaining and controlling pH of the electroless nickel plating solution Do. Therefore, the second pH adjusting agent may be added to the electroless nickel plating solution as a substance that performs this function. The second pH adjuster may include an inorganic acid or a salt thereof such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, diethylenetriamine and the like. In particular, the second pH adjuster may exclude ammonia.
The second pH adjuster can maintain the pH of the electroless nickel plating solution at a basic level, for example, maintain the pH range from 7.5 to 12, for example, maintain the pH range from 8 to 11, For example, the pH range can be maintained between 8.5 and 10.5. If the pH value of the electroless nickel plating solution is less than 8.0 or more than 11, the plating rate is decreased, and the properties of the plating layer may be lowered or the stability of the plating solution may be decreased.
Hereinafter, experimental examples practically implementing the continuous electroless plating method of copper and nickel according to the technical idea of the present invention will be described.
≪ Pretreatment of plating object &
The surfaces of the fibers to be plated were pretreated as follows using the continuous electroless plating method of copper and nickel according to the technical idea of the present invention. The pretreatment may include an etching step, a surface modification step, a catalyst treatment step, and a reduction step.
First, the plating object was immersed in an etching agent (IPC-101) of Incheon Chemical Company at a temperature of about 40 캜 for about 5 minutes. After the completion of the etching, the plating object was washed with water. Subsequently, the plating target was immersed in a pretreatment agent (CP-9000) at a temperature of about 60 DEG C for about 5 minutes to easily carry out surface modification of the catalyst on the plating target. After completion of the surface modification, the plating object was washed with water. Subsequently, the plating object was immersed in a catalyst (PCT-640) at a temperature of about 60 DEG C for about 5 minutes to carry out a catalyst treatment for adsorbing the catalyst to the plating object. After completion of the catalyst treatment, the plating object was washed with water. Subsequently, the plating object was immersed in an activator (PCT-646) at room temperature (at a temperature of about 25 캜) for about 5 minutes to reduce the plating object to complete the pretreatment step. After the completion of the reduction treatment, the plating object was washed with water. The water rinsing between the treatment steps was carried out in two cycles.
<Formation of copper plating layer>
The pre-treated object to be plated was immersed in an electroless copper plating solution to perform electroless copper plating to form a copper plating layer.
The electroless copper plating solution used copper sulfate as a copper metal salt, and the concentration of copper ions in the electroless copper plating solution was adjusted to 3 g per 1 liter of the electroless copper plating solution. The first reducing agent used was 20 g of sodium hypophosphite per liter of the electroless copper plating solution and 5 g of glyoxylic acid per liter of the electroless copper plating solution. The first complexing agent was prepared by mixing 10 g of N, N, N, N'-tetrakis (2-hydroxypropyl) ethylenediamine (THPED) and 1 liter of the electroless copper plating solution per liter of the electroless copper plating solution 10 g of citric acid was used. As the stabilizer, 2 mg of sodium cyanide was used per 1 liter of the electroless copper plating solution.
The temperature of the electroless copper plating solution was 50 캜, the pH was 12.5, and the copper plating rate was about 2 탆 / hour.
<Formation of Nickel Plating Layer: Experimental Example 1>
The object to be plated with the copper plating layer was immersed in an electroless nickel plating solution to perform electroless nickel plating to form a nickel plating layer on the copper plating layer.
In Experimental Example 1, the electroless nickel plating solution used nickel sulfate as the nickel metal salt, and the nickel ion in the electroless nickel plating solution was adjusted to 4 g with respect to 1 liter of the electroless nickel plating solution. As the second reducing agent, 16 g of sodium hypophosphite was used per 1 liter of the electroless nickel plating solution. As the second complexing agent, 5 g of citric acid and 1 g of the electroless nickel plating solution were used in an amount of 5 g of glycine per liter of the electroless nickel plating solution.
The temperature of the electroless nickel plating was 50 캜, the pH adjusted with sodium hydroxide was 9, and the nickel plating rate was about 3.3 탆 / hour.
For reference, when only sodium citrate is used as the second complexing agent in the case of using sodium hydroxide as the second pH adjusting agent in the electroless nickel plating solution, the stability of the electroless nickel plating solution may be decreased according to the pH of the electroless nickel plating solution , So that the electroless nickel plating solution can easily be self-decomposed. On the other hand, when only glycine is used as the second complexing agent, the stability of the electroless nickel plating solution is increased, but since the content of phosphorus in the nickel plating layer is low, it is easy to realize the phosphorus type nickel plating layer having a low phosphorus content. It may be difficult to implement an electroless nickel plating layer of a relatively high type or a high type.
<Formation of Nickel Plating Layer: Experimental Example 2>
In Experimental Example 2, in comparison with Experimental Example 1, there was a difference in using tartaric acid instead of citric acid as the second complexing agent, and the rest was performed under the same conditions. Specifically, in Experimental Example 2, 5 g of tartaric acid and 5 g of glycine were used per 1 liter of the electroless nickel plating solution and 1 liter of the electroless nickel plating solution.
The nickel plating rate was about 3.4 탆 / hour. The content of phosphorus (P) vacated in the nickel plating layer was 3.3 wt.%.
<Formation of Nickel Plating Layer: Experimental Example 3>
In Experimental Example 3, as compared with Experimental Example 1, the second complexing agent had a difference in the concentration of glycine, and the remainder was performed under the same conditions. Specifically, in Experimental Example 3, in the second complexing agent, 15 g of glycine was used per liter of the electroless nickel plating solution and 5 liters of citric acid and 1 liter of the electroless nickel plating solution.
The nickel plating rate was about 2.5 탆 / hour. The content of phosphorus (P) vacated in the nickel plating layer was 6.5 wt%.
≪ Nickel Plating Layer Formation: Experimental Example 4 >
In Experimental Example 4, there was a difference in using succinic acid instead of citric acid and glycine as the second complexing agent in comparison with Experimental Example 1, and the rest was performed under the same conditions. Specifically, in Experimental Example 4, 10 g of succinic acid was used as the second complexing agent with respect to 1 liter of the electroless nickel plating solution.
The nickel plating rate was about 2.0 탆 / hour. The content of phosphorus (P) vacated in the nickel plating layer was 13.0 wt.%.
According to the present invention, it is possible to control the amount of vacancy of phosphorus to be deposited in the nickel plating layer by controlling the kind and content of the complexing agent contained in the electroless nickel plating solution. That is, the amount of phosphorus in the phosphorus can be controlled to be low (1 to 4 wt% phosphorus), (5 to 12 wt% phosphorus) and dead phosphorus (13 to 20 wt% phosphorus).
2 is a photomicrograph showing a copper plating layer formed using a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
2 (a) is a copper plating layer when formalin is used as a comparative example, and FIG. 2 (b) is a copper plating layer when formalin is not used as an embodiment of the present invention. FIG. 2 (b) was produced by the method described in the above-mentioned <copper plating layer formation>, and FIG. 2 (a) was prepared under the same conditions except that the first reducing agent was formalin.
Referring to FIG. 2, it can be seen that a copper plating layer is formed on a plating target material of a fiber material, both with and without formalin. Therefore, it can be understood that the method of forming the copper plating layer using the electroless copper plating liquid excluding formalin according to the technical idea of the present invention forms a copper plating layer having excellent properties.
3 is a photomicrograph showing a nickel plating layer formed using a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
3 (a) is a nickel plating layer formed on a copper plating layer in the case of using formalin and ammonia as a comparative example, and FIG. 3 (b) ≪ / RTI > 3 (b) is a graph showing the results obtained by the method described in <Formation of Nickel Plating Layer: Experimental Example 1> described above. FIG. 3 (a) shows the results obtained by using formalin as the first reducing agent and using ammonia as the second pH adjusting agent Were produced under the same conditions.
Referring to FIG. 3, it can be seen that a nickel plating layer is formed on the copper plating layer with both the formalin and ammonia being used and the nickel plating layer being very fine and almost free from defects. Therefore, it can be seen that the method of forming the nickel plating layer using the electroless nickel plating solution excluding ammonia according to the technical idea of the present invention forms a nickel plating layer having excellent properties.
FIG. 4 is a photograph showing color change of an electroless nickel plating solution used in a continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
Referring to FIG. 4, (a) shows the state of electroless nickel plating solution before performing electroless nickel plating, and the electroless nickel plating solution has a blue color. (b) shows the state of the electroless nickel plating solution after performing the electroless nickel plating for 30 minutes. The electroless nickel plating solution has pale blue according to consumption of nickel, and the stability of the electroless nickel plating solution is maintained Able to know. (c) shows the state of the electroless nickel plating solution after performing the electroless nickel plating for 1 hour and 30 minutes, and it turned into a clear solution as nickel was almost completely consumed. (d) shows that the electroless nickel plating solution replenished with a transparent electroless nickel plating solution and has a blue color similar to that of (a), and thus the stability of the electroless nickel plating solution is maintained even after the replenishment
As a result of the experiment shown in FIG. 4, in order to test the stability of the electroless nickel plating solution according to the technical idea of the present invention using sodium hydroxide without using ammonia water as the pH adjusting agent, the plating solution life test was conducted. As a result, The plating solution was stable even in the case of the transparent plating solution color, and the plating rate and stability of the plating solution were maintained when the nickel salt, the reducing agent, the complexing agent and the additive were mixed in the plating solution.
The method for replenishing the electroless nickel plating solution is as follows. In order to prolong the service life of the basic electroless nickel plating solution not containing ammonia water, 1 g / L of nickel ion is added every 1 g / L of nickel ion in the electroless nickel plating solution is consumed By adding 2 to 4 g / L of a reducing agent, adding 2 to 4 g / L of a first kind of complexing agent in the complexing agent and adding 1 to 2 g / L of a second kind of complexing agent, The nickel plating solution can be replenished by the year. Further, 0.1 to 2.0 ppm of Tl as a metal additive may be further added as an additive for improving the lifetime of the electroless nickel plating solution and the gloss of the plating layer. It is preferable that the replenishing time of the electroless nickel plating solution is supplemented at the time when the nickel ion of the electroless nickel plating solution is consumed at about 1/5 of the nickel concentration is the most preferable for the extension of the life of the electroless nickel plating solution and the formation and properties of the plating layer . The thallium may be added before the electroless nickel plating solution is used, or may be added at least once after use. Thallium is exemplified as a metal additive, and the technical idea of the present invention is not limited thereto.
FIG. 5 is a graph showing the weight of the plating layer formed on the electroless nickel plating solution used in the continuous electroless plating method of copper and nickel according to an embodiment of the present invention.
Referring to FIG. 5, as a result of supplementing the consumed plating solution as the use time of the electroless nickel plating solution was increased, the stability of the plating solution was maintained regardless of the number of times of plating (MTO, Metal turn over) Is also stably maintained.
The continuous electroless plating method of copper and nickel according to the technical idea of the present invention is a method of continuously forming a copper plating layer and a nickel plating layer on a nonconductive plating object by using an electroless copper plating liquid excluding formalin and an electroless nickel plating liquid excluding ammonia can do.
In performing electroless copper plating, by using sodium hypophosphite, glyoxylic acid, or the like instead of formalin which is conventionally used as a reducing agent, it is possible to form a copper plating layer having excellent properties while ensuring stability of the plating liquid, And the use of formaldehyde, which is harmful to the environment, can be essentially eliminated.
In addition, during the electroless nickel plating, by using citric acid, glycine, tartaric acid, succinic acid, or the like instead of ammonia, which is commonly used as a pH adjuster, a nickel plating layer having excellent properties is formed while securing stability of the plating solution, It is possible to fundamentally eliminate the use of ammonia which increases the lifetime and harms the operator and the environment.
The continuous electroless plating method of copper and nickel according to the technical idea of the present invention can effectively form a plating layer on a nonconductive plating object and thus can produce an electromagnetic wave shielding fiber product and the like, It can be used in various industrial fields such as electromagnetic shielding agents for electromagnetic wave shielding of industrial and electronic parts, static eliminators, surface heating elements, and functional clothes.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. Will be apparent to those of ordinary skill in the art.
Claims (21)
Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer; And
Immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer;
Lt; / RTI >
Wherein the first reducing agent is selected from the group consisting of glyoxalic acid, methylglyoxal, ethylglyoxal, benzaldehyde, glucose, fructose, galactose, maltose, lactose, phosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, Boron sodium, or mixtures thereof,
Wherein the first reducing agent is a mixture of two or more and five or less species,
Wherein the second pH adjuster comprises at least one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, and diethylenetriamine,
Wherein the first reducing agent is constituted by excluding formalin and the second pH adjusting agent is constituted by excluding ammonia,
Wherein the second complexing agent is at least one selected from the group consisting of copper, copper, copper, copper, copper, nickel, And a continuous electroless plating method of nickel.
Wherein the electroless copper plating solution and the electroless nickel plating solution have a basicity, and the continuous electroless plating method of copper and nickel.
Wherein the first complexing agent is a mixture of two or more and five or less species of the materials, and the continuous electroless plating method of copper and nickel.
Wherein the electroless copper plating solution is maintained at a temperature in the range of 10 캜 to 70 캜.
Wherein the electroless nickel plating solution is maintained at a temperature in the range of 20 占 폚 to 90 占 폚.
Wherein the nickel metal salt is contained in the range of 1 g to 10 g per 1 liter of the electroless nickel plating solution.
Wherein the second reducing agent comprises at least one of sodium hypophosphite, potassium hypophosphite, and ammonium hypophosphite,
Wherein the electroless nickel plating solution is contained in the range of 1 g to 100 g per 1 liter of the electroless nickel plating solution.
Wherein the electroless nickel plating solution has a pH in the range of 7.5 to 12.
Wherein the electroless copper plating solution contains copper sulfate as the copper metal salt and copper ions in the electroless copper plating solution are adjusted to a concentration of 3 g per liter of the electroless copper plating solution,
Wherein the first reducing agent comprises 20 g of sodium hypophosphite per liter of the electroless copper plating solution and 5 g of glyoxylic acid per liter of the electroless copper plating solution,
The first complexing agent is prepared by adding 10 g of N, N, N, N'-tetrakis (2-hydroxypropyl) ethylenediamine (THPED) to 1 liter of the electroless copper plating solution and 1 liter of the electroless copper plating solution Lt; RTI ID = 0.0 > 10 < / RTI > g of citric acid,
The stabilizer contained 2 mg of sodium cyanide per liter of the electroless copper plating solution,
Wherein the electroless copper plating solution has a temperature of 50 DEG C and a pH of 12.5.
Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer; And
Immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer;
Lt; / RTI >
Wherein the first reducing agent is selected from the group consisting of glyoxalic acid, methylglyoxal, ethylglyoxal, benzaldehyde, glucose, fructose, galactose, maltose, lactose, phosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, Boron sodium, or mixtures thereof,
Wherein the first reducing agent is a mixture of two or more and five or less species,
Wherein the second pH adjuster comprises at least one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, and diethylenetriamine,
Wherein the first reducing agent is constituted by excluding formalin and the second pH adjusting agent is constituted by excluding ammonia,
Wherein the electroless nickel plating solution contains nickel sulfate as the nickel metal salt and nickel ions in the electroless nickel plating solution are adjusted to a concentration of 4 g per 1 liter of the electroless nickel plating solution,
The second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution,
The second complexing agent comprises 5 g of citric acid per liter of the electroless nickel plating solution and 5 g of glycine per liter of the electroless nickel plating solution,
Wherein the electroless nickel plating solution has a temperature of 50 캜 and a pH of 9, wherein the electroless plating solution is copper and nickel.
Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer; And
Immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer;
Lt; / RTI >
Wherein the first reducing agent is selected from the group consisting of glyoxalic acid, methylglyoxal, ethylglyoxal, benzaldehyde, glucose, fructose, galactose, maltose, lactose, phosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, Boron sodium, or mixtures thereof,
Wherein the first reducing agent is a mixture of two or more and five or less species,
Wherein the second pH adjuster comprises at least one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, and diethylenetriamine,
Wherein the first reducing agent is constituted by excluding formalin and the second pH adjusting agent is constituted by excluding ammonia,
Wherein the electroless nickel plating solution contains nickel sulfate as the nickel metal salt and nickel ions in the electroless nickel plating solution are adjusted to a concentration of 4 g per 1 liter of the electroless nickel plating solution,
The second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution,
Wherein the second complexing agent comprises 5 g of tartaric acid per liter of the electroless nickel plating solution and 5 g of glycine per liter of the electroless nickel plating solution,
Wherein the electroless nickel plating solution has a temperature of 50 캜 and a pH of 9, wherein the electroless plating solution is copper and nickel.
Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer; And
Immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer;
Lt; / RTI >
Wherein the first reducing agent is selected from the group consisting of glyoxalic acid, methylglyoxal, ethylglyoxal, benzaldehyde, glucose, fructose, galactose, maltose, lactose, phosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, Boron sodium, or mixtures thereof,
Wherein the first reducing agent is a mixture of two or more and five or less species,
Wherein the second pH adjuster comprises at least one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, and diethylenetriamine,
Wherein the first reducing agent is constituted by excluding formalin and the second pH adjusting agent is constituted by excluding ammonia,
Wherein the electroless nickel plating solution contains nickel sulfate as the nickel metal salt and nickel ions in the electroless nickel plating solution are adjusted to a concentration of 4 g per 1 liter of the electroless nickel plating solution,
The second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution,
The second complexing agent comprises 15 g of glycine per 1 liter of the electroless nickel plating solution and 5 g of citric acid per 1 liter of the electroless nickel plating solution,
Wherein the electroless nickel plating solution has a temperature of 50 캜 and a pH of 9, wherein the electroless plating solution is copper and nickel.
Immersing the plating object in an electroless copper plating solution containing a copper metal salt, a first reducing agent, a first complexing agent, a first pH adjusting agent, and a stabilizer to form a copper plating layer; And
Immersing the plating object in an electroless nickel plating solution containing a nickel metal salt, a second reducing agent, a second complexing agent, and a second pH adjusting agent to form a nickel plating layer on the copper plating layer;
Lt; / RTI >
Wherein the first reducing agent is selected from the group consisting of glyoxalic acid, methylglyoxal, ethylglyoxal, benzaldehyde, glucose, fructose, galactose, maltose, lactose, phosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, Boron sodium, or mixtures thereof,
Wherein the first reducing agent is a mixture of two or more and five or less species,
Wherein the second pH adjuster comprises at least one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, and diethylenetriamine,
Wherein the first reducing agent is constituted by excluding formalin and the second pH adjusting agent is constituted by excluding ammonia,
Wherein the electroless nickel plating solution contains nickel sulfate as the nickel metal salt and nickel ions in the electroless nickel plating solution are adjusted to a concentration of 4 g per 1 liter of the electroless nickel plating solution,
The second reducing agent comprises 16 g of sodium hypophosphite per 1 liter of the electroless nickel plating solution,
Wherein the second complexing agent comprises 10 g of succinic acid per liter of the electroless nickel plating solution,
Wherein the electroless nickel plating solution has a temperature of 50 캜 and a pH of 9, wherein the electroless plating solution is copper and nickel.
In order to improve the lifetime of the electroless nickel plating solution and the gloss of the nickel plating layer, 0.1 to 2.0 ppm of thallium (Tl) is added at a point of time when nickel ions in the electroless nickel plating solution are consumed from 1/10 to 1/2 , A continuous electroless plating method of copper and nickel.
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| US20230323541A1 (en) * | 2020-11-10 | 2023-10-12 | Meltex Inc. | Electroless copper plating solution |
| CN117878196A (en) * | 2024-03-12 | 2024-04-12 | 深圳市松柏科工股份有限公司 | Manufacturing process of photovoltaic solar N-type oxide semiconductor ITO electroless copper plating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080093366A (en) * | 2007-04-16 | 2008-10-21 | 우에무라 고교 가부시키가이샤 | Electroless gold plating method and electronic parts |
| KR20110113349A (en) * | 2010-04-09 | 2011-10-17 | 한국생산기술연구원 | Electroless nikel plating solution, electroless plating method using the same and nikel coating layer prepared by the same |
| KR101206538B1 (en) * | 2012-07-19 | 2012-11-30 | 이을규 | Electroless copper plating solution and method for electroless copper plating |
| KR20130139426A (en) * | 2012-05-09 | 2013-12-23 | 권만천 | Manufacturing method of electroconductive fabric for electromagnetic interference(emi) shielding by using electroless |
-
2015
- 2015-04-08 KR KR1020150049777A patent/KR101660520B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080093366A (en) * | 2007-04-16 | 2008-10-21 | 우에무라 고교 가부시키가이샤 | Electroless gold plating method and electronic parts |
| KR20110113349A (en) * | 2010-04-09 | 2011-10-17 | 한국생산기술연구원 | Electroless nikel plating solution, electroless plating method using the same and nikel coating layer prepared by the same |
| KR20130139426A (en) * | 2012-05-09 | 2013-12-23 | 권만천 | Manufacturing method of electroconductive fabric for electromagnetic interference(emi) shielding by using electroless |
| KR101206538B1 (en) * | 2012-07-19 | 2012-11-30 | 이을규 | Electroless copper plating solution and method for electroless copper plating |
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| US20230323541A1 (en) * | 2020-11-10 | 2023-10-12 | Meltex Inc. | Electroless copper plating solution |
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| CN114959698A (en) * | 2022-06-30 | 2022-08-30 | 光华科学技术研究院(广东)有限公司 | Coating, method for the production thereof and component |
| CN115478266A (en) * | 2022-08-18 | 2022-12-16 | 胜宏科技（惠州）股份有限公司 | Activated immersion liquid used for carrier plate and method for chemically plating nickel and gold on carrier plate |
| CN115478266B (en) * | 2022-08-18 | 2024-01-05 | 胜宏科技（惠州）股份有限公司 | Post-activation immersion liquid for carrier plate and method for chemically plating nickel and gold on carrier plate |
| CN115522188A (en) * | 2022-09-02 | 2022-12-27 | 南通赛可特电子有限公司 | High-speed chemical copper plating solution and copper plating process thereof |
| CN115410925B (en) * | 2022-09-22 | 2023-08-11 | 江苏富乐华半导体科技股份有限公司 | Method for improving heat-resistant cycle reliability of aluminum nitride coated aluminum packaging lining plate |
| CN117878196A (en) * | 2024-03-12 | 2024-04-12 | 深圳市松柏科工股份有限公司 | Manufacturing process of photovoltaic solar N-type oxide semiconductor ITO electroless copper plating |
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